3-Acetyl-4-hydroxybenzyl phosphonates

ABSTRACT

Unsubstituted and substituted dialkyl esters of phosphonic and diphosphonic acids, nuclearly brominated derivatives thereof, and metal mono-, bis-, and tris- derivatives of phosphonic acid halfesters are useful as ultraviolet light absorbers and as fire retardants.

baited @ates Patent [191 Fenyes et al.

[ ]Mar. 18, 1975 E L- -HX R YBEEZLYL PHOSPHONATES Inventors: Joseph G. E. Fenyes; Kenneth J.

Flanagan, both of Memphis, Tenn.

Assignee: Buckman Laboratories, Inc., Memphis, Tenn.

Filed: Oct. 3, 1973 Appl. No.: 399,022

Related US. Application Data Continuation of Ser, No. 168,744, Aug. 3, 1971, abandoned, which is a continuation-in-part of Ser. No. l27,776, March 24, 1971, Pat. No. 3,767,735.

US. Cl 260/946, 44/68, 44/DlG. 4, 252/497, 252/498, 252/400, 260/45.7, 260/45.75 R, 260/45.75 N, 260/398.5, 260/429.7, 260/429.9, 260/439, 260/448 R, 260/969 Int. Cl. C07f 9/40, C08f 45/58 Field of Search 260/946 References Cited UNITED STATES PATENTS l/l969 Schenerer et al 260/946 Primary Examiner-Anton H. Sutto Attorney, Agent, or Firm-Floyd E. Trimble 57] ABSTRACT 3 Claims, No Drawings 3-ACETYL-4-HYDROXYBENZYL PHOSPHONATES This is a continuation application of Patent application Ser. No. 168,744, filed Aug. 3, 1971 now abandoned, which in turn is a continuation-in-part of Patent application Ser. No. 127,776, filed Mar. 24, 1971, now US. Pat. No. 3,767,735.

This invention relates to novel derivatives of phosphonic and diphosphonic acids, their preparation and use as ultraviolet light absorbers and as fire retardants. More particularly, the present invention relates to the preparation and use of the novel compounds of our invention which may be defined as phosphonic acid derivatives selected from the class consisting of unsubstituted and substituted dialkyl esters of phosphonic and diphosphonic acids, nuclearly brominated derivatives thereof, and metal mono-, bis-, and tris-[(O-alkyl)-3- acetyl-4-hydroxybenzyl] phosphonates.

It is well known that many organic compositions such as polymeric organic compositions tend to undergo deterioration when exposed to ultraviolet light. Light in the ultraviolet portion ofthe spectrum and particularly that having a wavelength within 290-400 millimicrons causes photocatalyzed changes, such as yellowing and- /or embrittlement of unstabilized polymeric compositions. These changes are obviously undesirable and this is particularly true when the composition is initially colorless, transparent, or translucent and is to be used subsequently under conditions that will subject it to long exposure to sunlight or other sources of ultraviolet light radiation. Examples of such applications include translucent roofing materials, transparent structures, decorative structures, decorative and protective coatings, and impact-resistant windows.

In recent years, many organic compounds have become available which can absorb ultraviolet light and convert it to less harmful forms of energy such as heat, vibrational energy, or less harmful radiation. These organic stabilizers, in addition to absorbing ultraviolet radiation in the selected range for the polymeric compositions being treated, must be compatible therewith, have little or no initial color, be reasonably inexpensive, be chemically stable, and have a low toxicity, es pecially for stabilizing compositions to be used subsequently in the food industry.

A good ultraviolet absorber for use in polymeric organic compositions should absorb the ultraviolet radiation in daylight, impart no or very little color to the composition, should be sufficiently stable to withstand curing conditions, and should absorb ultraviolet light sufficiently to protect the composition against yellowing and decomposition on exposure to ultraviolet light. The compound must have sufficient solubility in various types of materials so that it may be incorporated therein, it should be capable of withstanding leaching action of solvents or loss by exudation.

Generally, an effective ultraviolet absorber should have its peak absorption above a wavelength of 300 millimicrons or the absorption peak may be at a higher wavelength as long as the absorption drops off sufficiently as it approaches the visual range so that no color is visible. in addition, to be effective it should show a high degree of absorbancy in the desired wavelength range, especially at those wavelengths sufficiently below the visual range so that the compound has no yellow color.

Although, as pointed out above, many compounds have been suggested for the stabilization of polymeric organic compositions against deterioration caused by ultraviolet light, none have been entirely satisfactory as all have been deficient in one or more qualities which the ideal ultraviolet absorber must possess. These include, in addition to lack of color, the ability to become firmly incorporated in the composition to be stabilized and the ability to absorb ultraviolet light over a wide range. The latter is important because individual polymeric organic compositions are generally most susceptible to deterioration by radiation of a specific wavelength. For example, polyethylene, polypropylene, and polystyrene are susceptible to radiation wavelengths of 300-320 millimicrons. Many of the absorbers disclosed in the prior art exhibit excellent ultraviolet light absorption only over a very limited wavelength. Another criteria of a polymeric organic composition in addition to its resistance to deterioration on exposure to ultraviolet light is that it be as resistant to fire as possible.

Heretofore when it was necessary to protect polymeric organic compositions against deterioration caused by exposure to ultraviolet light and to impart fire retardant properties to the composition, the use of two additives was mandatory; one to protect the composition against ultraviolet light and the other to attain the desired fire-retardant properties. This is objectionable because when two additives are used, each must not only perform its particular function effectively, but, in addition, the two must be compatible. Obviously, a single compound effective both as an ultraviolet light absorber and as a fire-retardant would eliminate completely the compatibility requirement and for that reason be desirable.

It is, therefore, a principle object of the present invention to provide an additive for polymeric organic compositions which is effective as an ultraviolet light absorber and is capable of rendering such compositions fire-retardant.

It is another object of our invention to provide a composition which is resistant to degradation by ultraviolet light radiation and is fire resistant.

These and other objects and advantages will become apparent as the description proceeds.

To the accomplishment of the foregoing and related ends, this invention then comprises the features hereinafter fully described and particularly pointed out in the claims, the following description setting forth in detail certain illustrative embodiments of the invention, these being indicative, however, of but a few of the various ways in which the principles of the invention may be employed.

In brief, the foregoing objects and advantages are obtained by incorporating into a polymeric organic composition susceptible to deterioration by the action of ultraviolet light radiation a compound identified generically as unsubstituted and substituted dialkyl esters of phosphonic and diphosphonic acids, nuclearly brominated derivatives thereof, and metal mono-, his, and tris-[(O-alkyl)-3-acetyl-4-hydroxybenzyllphosphonates in an amount varying from 0.1 to 5.0 percent by weight based on the total weight of the polymeric organic composition. When the compounds of our invention are employed as a fire retardant, the amount used may vary from 1 to 15 percent. It is understood, of course, that larger quantities of the phosphonate may be used, but such is not generally desirable because formula:

av c P 0 R 11 o-a c=o wherein R is a straight or branched chain alkyl radical containing from 1 to 18 carbon atoms. This alkyl group may be unsubstituted wherein the substituent is a halogen. R is an alkyl radical as defined for R with the further provision that R may also represent a metal having a valence of l to 3, n is an integer varying from 1 to 3, and X is bromine, hydrogen, methylene dialkyl phosphonate. or methylene bis-beta-chloroethyl phosphonate. Alternately, the latter group may be represented by the radical:

0 /OR C11 2 oa wherein R is as identified above.

Polymeric organic compositions which can be protected from the degrading effects of ultraviolet light and fire by the use ofthe compositions of our invention include alkyd resins as disclosed in US. Pat. Nos. 1.847.783. 1.860.164, 1,950,468, and 2,087,852; epoxy resins as disclosed in US. Pat. No. 2,886,473; polyester resins; polyurethane; polyethylene; polypropylene; polystyrene; polyvinyl chloride resins; cellulosic and acrylic polymers; linear super polyamide obtained by condensing an aliphatic polyethylenediamine with a dicarboxylic acid; industrial coatings including decorative and protective coatings wherein one or more of the components thereof comprises an organic composition susceptible to deterioration when exposed to ultraviolet light and/or coated fabrics such as fabrics coated with polyvinyl chloride and polyolcfin; and polyvinylidene chloride monofilaments.

In order to disclose the nature of the invention still more clearly. the following illustrative examples will be given. It is understood, however, that the invention is not to be limited to the specific conditions or details set forth in these examples. except insofar as such limitations are specified in the appended claims.

In the examples, parts where used are parts by weight.

EXAMPLE 1 Di-(n-butyl-3-acetyl-4-hydroxybenzyl phosphonate A l-liter, four neck, round-bottom flask equipped with stirrer. condenser, thermometer, and gas inlet was charged with 75.0 grams (0.3 mole) of tri-(nbutyllphosphite and 55.4 grams (0.3 mole) of 5'- 6O chloromethyl-Z'-hydroxyacetophenone. The mixture was purged for 5 minutes with nitrogen while stirring and then gently heated to -70 C., at which point exothermicity set in and butyl chloride distilled at about 76 to 79 C. The mixture was then heated to ap- 6 proximately -l10 at atmospheric pressure to complete the distillation ot butyl chloride and then distilled under vacuum to yield the product di-(n-butyl)-3- acetyl-4-hydroxybenzyl phosphonate, b.p. C./0.l5 mm.

EXAMPLE 2 Sodium [(O-butyl)-3-acetyl-4-hydroxybenzylIphosphonate A l-liter. four neck, round-bottom flask equipped with stirrer, reflux condenser, thermometer. and gas inlet was charged with 75.0 grams (0.215 mole) of di- (n-butyl)-3-acetyl-4-hydroxybenzyl phosphonate prepared in Example 1, to which was then added 34.4 grams of a 50 percent aqueous sodium hydroxide solution in 32.5 milliliters of methanol under nitrogen. After five minutes of purging with nitrogen. the nitrogen stream was stopped and the reaction mixture was refluxed 4.5 hours, after which time it was cooled to room temperature and neutralized with concentrated HCl to pH 7 with cooling. The precipitated sodium chloride was removed by filtration and washed with a small amount ofisopropyl alcohol. The washing and filtrate were combined and concentrated under reduced pressure. The dry residue was dissolved in a small amount of methyl alcohol and the insoluble solids. identified as sodium chloride, were removed by filtra tion. The filtrate was evaporated in vacuo to dryness. m.p. 193l95 C. This product was used without any further purification for the preparation of nickel and tin salts.

EXAMPLE 3 Preparation of nickel bis-1(O-butyl )-3-acetyl-4-hydroxybenzyl phosphonate A l-liter, three neck, round-bottom flask equipped with stirrer, reflux condenser, and thermometer was charged with 9.2 grams (0.029 mole) of sodium [(0- butyl)-3-acetyl-4-hydroxybenzyllphosphonate prepared in Example 2 dissolved in 100 milliliters of methanol to which was then added 3.6 grams (0.015 mole) ofnickelous chloride hexahydrate dissolved in 20 milliliters of methanol. The reaction mixture was stirred and heated at reflux for a period of 1 hour. after which it was filtered and the filtrate evaporated to dryness under vacuum. The pale green product did not melt up to 300 C. Anal. calculated for C- H Nio P- z P. 9.84 percent; Ni. 9.33 percent. Found; P, 9.68 percent; Ni. 9.13 percent.

EXAMPLE 4 Diethyl-3-acetyl-4-hydroxybenzyl phosphonate The foregoing compound was prepared following the same experimental procedure as used in Example 1. In this example. 92.3 grams (0.5 mole) of 5'- chlorometliyl-2'-hydroxyacetophenone was reacted with 83.0 grams (0.5 mole) of triethyl phosphite. The crude yellow product obtained was purified by distillation. The colorless liquid obtained as a distillate and identified by its infrared spectrum as diethyl-3-acetyl- 4-hydroxybenzyl phosphonate weighed 111.5 grams. This represented a yield of 77.9 percent of theory.

If desired. the reaction may be carried out in the presence of an inert solvent such as benzene. toluene. xylene, or chloroform. This modification of the experimental procedure lessens the vigor of the reaction.

EXAMPLE 5 Sodium {(O-ethyl )-3-acetyl-4-hydroxybenzyl ]phosphonate The foregoing compound was prepared following the same experimental procedure as used in Example 2. In this example, the product of Example 4 (111.5 grams) was reacted with 62.4 grams of a 50 percent aqueous sodium hydroxide solution to produce 68.0 grams of an off-white product identified as crude sodium ethyl)-3-acetyl-4-hydroxybenzyl]phosphonate. This product had a melting point of2l0220 C. and represented a yield of 62.4 percent of theory.

EXAMPLE 6 Nickel bis-[ O-ethyl )-3-acetyl-4-hydroxybenzyl]phosphonate The same experimental procedure as that used in Example 3 was used, in which 14.0 grams (0.05 mole) of sodium l(O-ethyl)-3-acetyl-4-hydroxybenzyl]- phosphonate was reacted with 6.0 grams (0.025 mole) of nickelous chloride hexahydrate. A pale green compound weighing 8.2 grams (57.4 percent) and having a melting point higher than 300 C. was obtained. Anal. calculated for C H NiO P: P, 10.81 percent; Ni, 10.24 percent. Found: P, 9.58 percent; Ni, 9.19 percent.

EXAMPLE 7 Di( isopropyl)-3-acetyl-4-hydroxybenzyl phosphonate The same experimental procedure was used in Examples l and 4 was used. In this example, 92.3 grams (0.5 mole) of 5'-chloromethyl-2-hydroxyacetophenone was reacted with 104.1 grams (0.5 mole) of triisopropyl phosphite. The reaction can also be carried out in an inert solvent such as benzene, toluene, xylene, or chlorobenzene to moderate the vigor of the reaction. The crude product, 142 grams (90.6 percent) was used in Example 8 without any further purification.

EXAMPLE 8 Sodium lO-isopropyl-3-acetyl-4-hydroxybenzyl)phosphonate The same experimental procedure as used in Examples 2 and 5 was used. In this example, 157.1 grams .0.5 mole) of di(isopropyl-3-acetyl-4-hydroxybenzyl phosphonate was used with 80.0 grams of 50 percent aqueous NaOH. The crude sodium (O-isopropyl-3- acetyl-4-hydroxybenzyl)phosphonate so obtained weighed 139 grams, representing a yield of 94.5 percent of theory.

EXAMPLE 9 Nickel bis-[(O-isopropyl)-3-acetyl-4-hydroxybenzyl]phosphonate was identified by characteristic peaks in its infrared spectrum as nickel bis-(Oisopropyl)-3-acetyl-4- hydroxybenzyl)phosphonate, m.p. 300 C.

EXAMPLE l0 Di(isooctyl)-3-acetyl-4-hydroxybenzyl phosphonate In this example the experimental procedure of Examples l, 4, and 7 was followed. Forty-six and one tenth grams of 5-chloromethyl-2-hydroxyacetophenone (0.25 mole) was treated with 104.6 grams (0.25 mole) of triisooctyl phosphite. After the reaction was completed, the crude di(isooctyl)-3-acetyl-4- hydroxybenzyl phosphonate was used directly without further purification for the preparation of the sodium salt of the corresponding half-ester.

EXAMPLE 1 1 Sodium O-isooctyl-3-acetyl-4-hydroxybenzyl )phosphonate The same experimental procedure as used in Examples 2, 5, and 8 was used to treat 114 grams (0.25 mole) of di(isooctyl-3-acetyl-4-hydroxybenzyl phosphonate in 100 milliliters of methanol with 40 grams of 50 percent aqueous sodium hydroxide to give 77 grams (84.5 percent yield) of sodium (O-isooctyl-3-acetyl-4- hydroxybenzyl)phosphonate. This compound was identified by spectroscopic method.

EXAMPLE 12 Nickel bis-[(O-isooctyl)-3-acetyl-4-hydroxybenzyllphosphonate The same experimental procedure as used in Examples 3, 6, and 9 was used to react 91.1 grams (0.25 mole) of sodium (O-isooctyl-3-acetyl-4-hydroxybenzyl)-phosphonate with 29.7 grams (0.25 mole) of nickelous chloride hexahydrate. Eighty-three grams percent yield) of nickel bis-[(O-isooctyl)-3-acetyl-4- hydroxybenzyl]phosphonate was obtained, m.p. 300 C.

EXAMPLE 1 3 Dimethyl-3-acetyl-4-hydroxybenzyl phosphonate The same experimental procedure as that used in Examples 1, 4, 7, and 10 was used to treat 184.6 grams (1.0 mole) of 5 '-chloromethyl-2 hydroxyacetophenone with 124 grams (1.0 mole) of trimethyl phosphite. This reaction was the most vigorous of all the reactions aimed at the preparation of a dialkyl-3-acetyl-4-hydroxybenzyl phosphonate. The reaction can be moderated by cooling once the evolution of methyl chloride is started. Alternately and somewhat preferably, the reaction may be carried out in an inert solvent such as benzene, toluene, xylene, or chlorobenzene. The product (240 grams, 93 percent) was identified by its characteristic infrared bands as dimethyl-3- acetyl-4-hydroxybenzyl phosphonate and was used without any further purification in the next reaction.

EXAMPLE 14 Sodium [(O-methyl )-3-acetyl-4-hydroxybenzyl]phosphonate The same experimental procedure as that used in Examples 2, 5, 8, and 11 was used to treat 240 grams (0.93 mole) of dimethyl-3-acetyl-4-hydroxybenzyl phosphonate with 148.8 grams of 50 percent aqueous sodium hydroxide. One hundred and sixty-four grams (69 percent yield) of a dark brown compound was obtained, m.p. 200-210 C.

EXAMPLE Nickel bis-l (O-methyl )-3-acetyl-4-hydroxybenzyl]phosphonate The same experimental procedure as that used in Examples 3, 6, 9. and 12 was used to react 48.5 grams (0.182 mole) of sodium [(O-methy1)-3-acetyl-4- hydroxybenzyl]phosphonate with 21.6 grams (0.091 mole) ofnickelous chloride hexahydrate. A green powdery product weighing 43 grams (87.4 percent yield) was obtained and was identified by its infrared spectrum as nickel bis-[(O-methyl )-3-acetyl-4-hydroxybenzyl]phosphonate, m.p. 300 C.

EXAMPLE 16 Aluminum tris-[ O-ethyl )-3-acetyl-4-hydroxybenzyl ]phosphonate EXAMPLE 17 Zinc bis-1(O-ethyl)-3-acetyl-4-hydroxybenzyl]phosphonate The same experimental procedure as that used in Example 16 was used to treat a suspension of 28 grams (0.1 mole) of sodium [(O-ethy1)-3-acetyl-4- hydroxybenzyl]phosphonate in 175 milliliters of methanol with a suspension of 6.8 grams (0.05 mole) of zinc chloride in approximately 50 milliliters of methanol. Twenty-five grams (86 percent yield) of a white powdery material was obtained and was spectroscopically identified as zinc bis-l(O-ethy1)-3-acetyl-4- hydroxybenzyl]phosphonate, m.p. 27075 C.

EXAMPLE 18 Barium bis-[ O-ethyl )-3-acetyl-4-hydroxybenzyl ]phosphonate The same experimental procedure as that used in Examples 16 and 17 was used to treat a solution of 28 grams (0.1 mole) of sodium [(O-ethy1)-3-acetyl-4- hydroxybenzyl]phosphonate with a suspension of 12.2 grams of barium chloride dihydrate in 75 milliliters of methanol. The suspension was filtered hot after two hours of refluxing and the filtrate evaporated under reduced pressure to give 24.0 grams (73.6 percent yield) of an off-white powdery product which was identified spectroscopically as barium bis-[(O-ethyl)-3-acetyl-4- hydroxybenzyl]phosphonate.

EXAMPLE l9 Cadmium bis-[(O-ethyl)-3-acetyl-4-hydroxybenzyl]phosphonate The same experimental procedure as that used in Examples l6 and 17 was used to react a solution of 28 grams (0.1 mole) of sodium [(O-ethy1)-3-acetyl-4- hydroxybenzyl]phosphonate in 200 milliliters of methanol with 9.2 grams (0.05 mole) of cadmium chloride in 50 milliliters of methanol. A white powder weighing 24 grams (67.7 percent yield) was obtained and was identified by its infrared spectrum as cadmium bis-[ (0- ethyl)-3-acetyl-4-hydroxybenzy1]phosphonate, m.p. 255-265 C.

EXAMPLE 20 Tin bis-l(O-ethyl)-3-acety1-4-hydroxybenzyl]phosphonate The same experimental procedure as that used in Examples 16, 17, and 19 was used to react a solution of 29.4 grams (0.14 mole) of sodium [(O-ethyl )-3-acet \'l- 4-hydroxybenzyl]phosphonate in 350 milliliters of methanol with 13.4 grams (0.07 mole) of stannous chloride. After 30 minutes of heating. the slurry was filtered and the white solid material was washed with water and air dried to give 31 grams (69.7 percent yield) of a white product which was identified by spectroscopic method to be tin bis-l(O-ethyl)-3-acetyl-4 hydroxybenzyl]phosphonate, m.p. 300 C.

EXAMPLE 21 Di(n-dodecy1)-3-acetyl4-hydroxybenzyl phosphonate The same experimental procedure as used in Examples 1. 4, 7, and 10 was used to react 58.6 grams (0.1 mole) of tri-(n-dodecyl)phosphite with 18.4 grams (0.1 mole) of 5-chloromethyl-2'-hydroxyacetophenone. The molten mixture was kept at c./0.5 mm. for 2 hours, then heated to approximately 180 C./0.5 mm. to remove dodecyl chloride. The residue was identified by its IR spectrum as di-(n-dodecyl)-3-acetyl-4- hydroxybenzyl phosphonate.

EXAMPLE 22 Sodium [(O-n-dodecyl )-3-acetyl-4-hydroxybenzyl ]phosphonate The same experimental procedure as that used in Examples 2, 5, 8, l l, and 14 was used for the preparation of the above sodium salt. The compound was identified by its infrared spectrum.

EXAMPLE 23 Nickel bis-l O-n-dodecyl )-3-acety1-4-hydroxybenzy1]phosphonate The same experimental procedure as that used in Examples 3, 6, 9, 12. and 15 was used to prepare nickel bis[(O-n-dodecy1)-3-acetyl-4-hydroxybenzy1]phosphonate. The compound was identified by its infrared spectrum.

EXAMPLE 24 Similarly by the use of trioctadecylphosphite and 5'- chloromethyl-2-hydroxyacetophenonen we obtained dioctadecyl-3-acetyl-4-hydroxybenzyl phosphonate.

This compound was identified by its infrared spectrum.

EXAMPLE 25 By following the experimental procedure described in Examples 2,5, 8, l1, and 14 we obtained sodium O-octadecyl )-3-acetyl-4-hydroxybenzyl phosphonate.

EXAMPLE 26 The same experimental procedure as used in Example 23 was used to prepare nickel bis-[(O-dioctadecyl)- 3-acetyl-4-hydroxybenzyllphosphonate, which was obtained as a light green powder. Identification was made by means of its infrared spectrum.

EXAMPLE 27 Bis-( 2-chloroethyl )-3-acetyl-4-hydroxybenzyl phosphonate A l-liter, four neck, round-bottom flask equipped with stirrer, condenser, thermometer, and a gas inlet tube was charged with 145.8 grams (0.789 mole) of chloromethyl-Z-hydroxyacetophenone. The flask was purged for 5-10 minutes with nitrogen while it was gently heated to 8590 C., at which point 212.8 grams (0.789 mole) of tris-(2-chloroethyl)phosphite was slowly introduced. Exothermicity set in and ethylene chloride distilled at 8485 C. After the addition was completed, the product was placed under vacuum to expel any ethylene chloride which remained entrapped in it. The product was identified by its infrared spectrum.

EXAMPLE 28 Diethyl-3-acetyl-5-bromo-4-hydroxybenzyl phosphonate A I-liter, four neck, round-bottom flask equipped with stirrer, reflux condenser, thermometer and a dropping funnel was charged with 286.2 grams (1.0 mole) of diethyl-3-acetyl-4-hydroxybenzyl phosphonate and 500 milliliters of water. The mixture was stirred and heated at 5358 C. while 168 grams (1.05 mole) of bromine was introduced over a period of 2 hours. The mixture was stirred and refluxed for an additional 2 hours, cooled to room temperature, and the aqueous layer (upper phase) discarded. The organic layer (lower phase) was dissolved in a mixture of chloroform and ether, dried over anhydrous MgSO filtered and concentrated under reduced pressure to give 358.5 grams (98.2 percent yield) ofa reddish-yellow, viscous liquid, which was identified as diethyl-3-acetyl-5- bromo-4-hydroxybenzyl phosphonate. Anal. calculated for C, H,,,BrO P: Br, 21.88 percent. Found: Br, 21.4 percent.

EXAMPLE 29 Preparation of bis(diethyl-5-acetyl-4-hydroxy)m-xylyl phosphonate A l-liter, four neck, round-bottom flask equipped with a stirrer, distilling head. condenser, thermometer,

and a dropping funnel was charged with 116.5 grams (0.5 mole) of 3, 5-bis-chloromethyl-2'- hydroxyacetophenone [(Gazz. chim. ital. 80, 502-9( 1950)] and about 10 milliliters of triethyl phos phite. The mixture was then stirred and heated to -80 C. at which temperature an additional quantity of triethyl phosphite was slowly introduced into the mixture until the total quantity of the phosphite used in the reaction was equal to 166.2 grams (1.0 mole). A greenish yellow viscous liquid weighing 193.7 grams (93.5 percent yield) was obtained. The product was identified by characteristic bands in its infrared spectrum as bis(diethyl-5-acetyl-4-hydroxy)m-xylyl phosphonate.

The compound bis(beta-chloroethyl-5-acetyl4- hydroxy)m-xylyl phosphonate was prepared by a similar procedure as follows: One hundred and sixteen and five tenths grams (0.5 mole) of 3, 5'-bis-chloromethyl- 2-hydroxyacetophenone was treated with 269.5 grams (1.0 mole) of tris-(2-chloroethyl)phosphite to give 241 grams (83.7 percent yield) of a viscous amber colored liquid identified by characteristic bands in its infrared spectrum as bis(beta-chloroethyl-5-acetyl-4- hydroxy)m-xylyl phosphonate.

EXAMPLE 3O Polypropylene resin In this example, the effect of the various phosphonate derivatives as identified in Samples No. 2 to 18 at two concentrations on a polypropylene film was determined. Sixteen such films were prepared as follows.

Sample No. 1, which contained parts unstabilized polypropylene, 0.1 part dilauryl thiodipropionate, and 1.0 part ofa hindered phenol was fused in a Plasti- Corder blender at 175 for 5 minutes. The hindered phenol used was a product available under the trademark Irganox 1076, which is an alkyl ester of a carboxylic acid containing an alkylhydroxy phenyl group. This product is further identified in US. Pat. No. 3.330.859. The fused material was chopped and the resulting gratiules pressed into sheets or films about 25 mils thick using a Carver press at about C.

Samples No. 2 to 18 were prepared by the same experimental procedure as used in the preparation of Sample No. 1 except that the various phosphonate derivatives in the amounts indicated in Table 1 were added to each sample before fusion.

The resulting films were then used to determine the effectiveness of the phosphonate derivatives as ultraviolet light absorbers by exposing the 18 films in chambers lighted with ultraviolet light and daylight fluorescent tubes for 575 hours. Each sample was exposed so that the film protected a portion of a light-colored maple tongue blade. After 575 hours exposure, the wood exposed directly to the light and the wood exposed behind the film of Sample No. 1 showed considerable darkening. The experiments together with the results are summarized in Table 1.

TABLE 1 Comparative effectiveness of various l(O-ulkyl)-3-acetyl-4-hydroxybenzyl]phosphonutes as ultraviolet light absorbers in polypropylene film after 575 hours exposure. Parts phosphonate Condition of film Samp l(O-alkyl)-3-acetyl-4-hydroxyadded per 100 UV No. benzyllphosphonate derivative parts polypropylene protection Clarity Color Flexibility 1 Control 0.0 None Clear Clear Brittle 2 Nickel bis-[(O-ethym 0.5 do. do. 81. yellow do.

Comparative effectiveness of various [(O-alkyl)-3-acetyl-4-hydroxybenzyllphosphonates as ultraviolet light absorbers in polypropylene film after 575 hours exposure.

Parts phosphonate Condition of film Samp [(O-alkyl)-3-acetyl-4-hydroxyadded per I No. benzyllphosphonate derivative parts polypropylene protection Clarity Color Flexibility 3 do. 1.0 Very slight do. Yellow Cracked 4 Tin bis-[(O-butyl)] 0.5 Good opalescent Sl. yellow Brittle 5 do. l.0 Very good do. do. do. 6 Nickel bis-[(O-isooctyl)] 0.5 Very slight Clear do. do. 7 do. 1.0 Slight do. do. Cracked 8 Nickel bis-[(O-isopropyl)] 0.5 do. do. do. do. 9 do. l.O Good do. do. do. [0 Barium bis-[(O-ethyl)] 0.5 Slight do. Very sl. yellow do. I I do. 10 Very good do. 5]. yellow Cracked less l2 Zinc bis-[(O-ethyh] 0.5 Slight do. Very sl. yellow Brittle l 3 do. I .0 Good do. do. do. 14 Cadmium bis-[(O-ethyl)] 05 Very slight do. Sl. yellow do. l5 do. l.0 Slight do. do. Cracked 16 Sodium [(O-ethyl)] 0.5 Slight do. Sl. tan do. 17 do. 1.0 Very good do. do. 8!. cracked l8 Diethyl-3-acetyl-4-hydroxybenzyl phosphonate l.0 Good do. SI. yellow Sl. cracked not brittle Table 2 Diethyl-3-acetyl-4-hydroxybenzyl phosphonate as a fire retardant for a polypropylene film.

Concentration in percent Burn time in Samby weight Time in secseconds before ple onds to burn self No. Phospho- Chlorowax 7O 4 inches extinguishing nate l 0 O 62 2 l O 69 3 2.5 O 64 4 O 5 76 5 0 IO 75 46 6 0 l5 72 41 7 l 5 91 45 8 l 10 90 2O 9 l 15 6 10 2.5 5 68 l l 2.5 10 5 12 2.5 15 4 l3 5 l0 4 l4 5 l5 2 15 7.5 5 16 7.5 l0 3 17 7.5 15 3 Self-extinguishing before burning 4 inches. "Combustible The foregoing data indicate that a combination comprising l to 5 percent of the phosphonate used in combination with 5 to 15 percent Chlorowax 70 is very effective as a fire retardant for polypropylene resin films.

The foregoing experiment was repeated in which a polyethylene resin film was substituted for that of the polypropylene. In this experiment, a combination comprising 3 percent phosphonate plus 10 percent Chlorowax 70 increased the time in seconds required to burn 4 inches to 233 seconds from 72 for the control.

The foregoing experiment was again repeated in which a halogenated (tetrachlorophthalic anhydride)- polyester resin film was substituted for that of the polypropylene. In this experiment, it was found that the use of Chlorowax did not contribute any beneficial results. The experiments together with the results are summarized in Table 3.

TABLE 3 Diethyl-3-acetyl-4-hydroxybenzyl phosphonate as a fire retardant for it halogenated polyester resin.

Burn time in Time in secseconds before Sample Concentration in percent onds to burn self- No. by weight of phosphonate 4 inches extinguishing l 0 I97 2 0.5 213 3 L0 204 97 4 2.0 5 3.0 5l 6 5.0 9 7 7.5 2 8 10.0 3 9 12.5 l.5 IO l5 l.(l

Self-extinguishing before burning 4 inches "Combustible EXAMPLE 3l Polyethylene resin In this example, the effect of the various phosphonate derivatives as identified in Samples 2 to 24 on a polyethylene film was determined. Twenty-four such films were prepared as follows.

Sample No. l was prepared by fusing 100 parts of polyethylene in a Plasticorder blender at 175 C. for 5 minutes. The fused material was chopped and the re sulting granules pressed into sheets or films about 25 mils thick using a Carver press at about C.

Samples N0. 2 to 24 were prepared by the same experimental procedure as used in the preparation of Sample No. 1 except that the various phosphonate derivatives in the amounts indicated in Table 4 were added to each sample before fusion.

The films were tested by exposure in a chamber lighted with ultraviolet light and daylight fluorescent tubes for a period of 575 hours. Each sample was exposed so that the film protected a portion of a lightcolored maple tongue blade. After 575 hours exposure, the wood exposed directly to the light and the wood exposed behind the film of Sample No. l showed considerable darkening. The experiments together with the results are summarized in Table 4.

TABLE 4 Comparative effectiveness of various [(O-alkyl)-3-acetyl-4-hydroxybenzyllphosphonates as ultraviolet light absorbers in polyethylene film after 575 hours exposure. Parts phosphonate Condition of film Sample [(O-alkyl-3-acetyl-4-hydroxyadded per lOO UV No. benzyllphosphonate derivative parts polyethylene protection Clarity Color Felxibility l Control 0.0 None Opaque Yellow Brittle Z Nickel bis-[(O-ethym 0.5 do. Opalescent White do. 3 do. 1.0 Very slight do. 8]. yellow No cracking 4 Tin bis-[(O-butyl)] 0.5 Slight do. White do. 5 do. 1.0 Very good do. do. do. 6 Nickel his-[(O-isooctyl)] 0.5 None do. do. Cracked do. l.0 Slight do. Sl. yellow No cracking 8 Nickel bis-[(O-isopropylH 0.5 Very 'ght do. do. Cracked 9 do. 1.0 Slight do. Yellow do. if) Barium bis-[(O-ethyl)] 0.5 Very slight do. White No cracking l I do. l.0 Good do. do. do. 12 Zinc bis-[(O-ethyl)] 0.5 Slight do. do. do. i 3 do. 1.0 Good do. do. do. 14 Cadmium bis-[(O-ethyl)] 0.5 None do. do. Cracked 5 do. l.0 Slight do. do. No cracking l6 Tin bis-[(O-ethyU] 0.5 None do. Splotchy Brittle 17 do. LO Very slight do. Yellow-splotchy Cracked 18 Aluminum tris-[(O-ethyl)] 0.5 Slight do. White do. l9 do. l.O Very good do. 51. yellow Less cracking 20 Nickel bis-[(O-ethyh] 0.5 None do. White Brittle 2| do. 1.0 Slight dov 8]. yellow 8]. cracking 22 Sodium [(O-ethyl)] 0.5 do. do. Sl. tan Cracked 23 do. 1.0 Good do. Tan 8]. cracking Z4 Diethyl-3-acetyl-4-hydroxybenzyl phosphonate l.O Good do. Sl. yellow \ery slight cracking not brittle EXAMPLE 32 Polyvinyl chloride resin in this example, a resinous composition was prepared which contained on a weight basis 100 parts polyvinyl chloride resin, 50 parts dioctyl phthalate, 1 part barium stearate, and 1 part cadmium stearate. This composition was divided into 21 equal portions. One was used as a control, and to portions 2 to 20 was added the phosphonate listed in Examples and 31 in such an amount that the weight percent of the phosphonate based on the weight of the polyvinyl chloride varied as follows: 0.5 and L0 percent.

The samples were laid over light-colored maple wood in a chamber lighted with fluorescent sunlight and ultraviolet light. Darkening of the wood occurred under the untreated plasticized polyvinyl chloride sample. No darkening occurred under the samples containing 0.5 and 1.0 parts of the phosphonates after 575 hours of light exposure. Further, the samples with 0.5 and 1.0 parts of the phosphonates exhibited less plasticizer surface exudation than the untreated sample after 575 hours of light exposure.

EXAMPLE 33 Coating compositions In this example, the phosphonates listed in Examples 30 and 31 were added to each of three different coating compositions of 50 percent solids identified as follows: Medium soya alkyd resin, air-dried polyurethane resin, and a tung oil varnish at concentrations of O, 0.5, and 1.0 percent by weight based on the total weight of the clear coating. These coatings were applied by brush to maple and Douglas fir wood surfaces. Two coats were applied allowing 24 hours between coats for drying. After the second coat had dried 24 hours, a small area of each coating on each of the wood surfaces was protected with a black tape and the coatings were exposed to ultraviolet light in an ultraviolet chamber.

After 50 hours exposure, the coatings that did not contain the phosphonate additives were badly discolored. Those coatings that contained 0.5 percent of the phosphonates were only slightly colored and the coatings containing 1.0 percent of the additivies exhibited no discoloration.

The nickel phosphonates disclosed in Examples 3. 6. 9, l2, 15, 23. and 26, especially when employed at a concentration equivalent to 1.0 percent based on the total weight of the resinous composition. exhibited excellent ultraviolet light absorbing properties.

The experiments reported in Examples 30 to 33 were repeated with the exception that sodium and potassium phosphonates were substituted for the various metal phosphonates used in those examples. Similar results were obtained.

In addition to their value as ultraviolet light absorbers for use with polymeric organic compositions. we have found that the phosphonates of our invention may be incorporated into consumer products such as face creams, lotions, and the like to protect the human skin from the detrimental effects of ultraviolet light.

Other materials which are stabilized by the compounds of the present invention include lubricating oil of the aliphatic ester type, e.g., di-(2-ethylhexyl)azelate, pentaerythritol tetracaproate and the like; animal and vegetable derived oils, e.g., linseed oil, fat, tallow, lard, peanut oil, cod liver oil, castor oil, palm oil. cottonseed oil, and the like; hydrocarbon materials such as gasoline, both natural and synthetic, diesel oil, mineral oil, fuel oil, cutting fluids, waxes, resins and the like; fatty acids; varnishes, soaps, and the like.

We have found that these phosphonates, especially the aluminum, barium, sodium, and zinc, are effective as heat stabilizers for polymeric organic compositions.

While particular embodiments of the invention have been described, it will be understood, of course, that the invention is not limited thereto since many modifications may be made thereto. lt is, therefore, contemplated to cover by the appended claims any such modifications as fall within the true spirit and scope of the invention.

The invention having thus been described, what is claimed and desired to be secured by Letters Patent is: 5

1. A compound having the formula:

each beta-chloroethyl. and X is hydrogen. 

1. COMPOUND HAVING THE FROMULA:
 2. The compound of claim 1 wherein R and R'' are each ethyl, and X is bromine.
 3. The compound of claim 1 wherein R and R'' are each beta-chloroethyl, and X is hydrogen. 